共聚法合成可熔纺聚丙烯腈树脂

综述了共聚法合成可熔纺的聚丙烯腈树脂的方法 ,介绍了国外主要的研究成果 ,讨论了自由基乳液聚合、悬浮聚合、交替共聚、活性聚合和模板聚合等聚合方法 ,并对这些方法进行了初步评价。指出自由基乳液聚合或悬浮聚合 ,应该是国内目前研究的重点 ,而原子转移自由基聚合有可能成为最有前途的可控聚合方法。     

纳米纤维素晶须表面接枝及其液晶性能研究进展

作为一种新兴的纳米生物材料,纳米纤维素日益受到各界的广泛关注,对其进行表面接枝改性并开发新的功能是十分必要的。本文综述了纳米纤维素晶须表面接枝的技术及研究进展,主要介绍了传统自由基聚合、离子和开环聚合及活性自由基聚合技术,包括氮氧自由基调控活性聚合、原子转移自由基聚合、可逆加成-断裂链转移聚合、单电子转移活性自由基聚合,讨论了各种接枝聚合方法的适用范围和优缺点。简述了点击化学在纳米纤维素晶须表面接枝的应用。通过各种聚合方法改性得到的纳米纤维素晶须接枝共聚物往往具有一些特殊的功能,某些接枝共聚物在适当的溶剂中可以形成液晶态,本文重点介绍了接枝改性的纳米纤维素晶须的液晶性能及其形成机理和影响因素等。     

纤维素系高吸水树脂的合成及种类

综述了纤维素系高吸水树脂的合成方法,介绍了游离基聚合,离子型聚合,缩合或加成反应聚合等几种合成方法,并对其种类进行的综述,最后对其发展前景进行了展望。     

超高相对分子质量聚(甲基)丙烯酸酯的制备及应用

介绍了制备超高相对分子质量聚(甲基)丙烯酸酯的常用方法,如等离子体引发自由基聚合、单电子转移-衰减链转移自由基聚合、反向原子转移自由基聚合、可逆加成-断裂链转移聚合、高压原子转移自由基聚合、金属催化活性自由基聚合等,分析了单体含量、催化剂种类和用量、引发剂种类和含量、反应温度、反应时间、反应压力等对合成超高相对分子质量聚(甲基)丙烯酸酯的影响,介绍了其良好的机械强度和透光性能以及其应用情况。认为超高相对分子质量聚(甲基)丙烯酸甲酯其韧性不足,极大地限制了其适用范围,如果将其与纳米材料复合改性将可以弥补这个缺点。复合改性的超高相对分子质量聚(甲基)丙烯酸甲酯将在有机玻璃及包覆材料等领域中具有非常广泛的应用前景。     

活性自由基乳液聚合的研究进展

活性自由基乳液聚合是一个非常新的研究领域。介绍了目前活性自由基乳液聚合领域的3种常用的方法及应用这些方法进行乳液聚合的研究进展,包括:原子转移自由基聚合(ATRP),氮氧调节自由基聚合(NMP)和可逆加成-断裂链转移自由基聚合(RAFT)。     

亲水性大分子单体的合成与应用述评

阐述了自由基聚合、原子转移自由基聚合、生物合成等亲水性大分子单体合成方法，介绍了聚乙烯吡啶等一些重要的亲水性大分子单体的合成，论述亲水性大分子单体在聚合物分子设计和改性方面的作用及在合成接枝聚合物、嵌段聚合物、高分子纳米微球和生命科学及医学领域中的应用。     

炭黑表面聚合物接枝改性的研究进展

介绍了各种单体通过自由基聚合、阴离子聚合、阳离子聚合等机理在炭黑表面的接技改性及活性聚合物在炭黑表面的接枝反应的研究进展,归纳了改性炭黑的性能及其表征方法。     

木质素的化学改性及其在高分子材料中的应用

概述了近年来木质素领域化学改性方法及其应用的研究进展,重点总结了木质素的接枝共聚改性方法,主要包括自由基聚合、开环聚合、自由基聚合,最后介绍了木质素在树脂材料、添加剂、聚氨酯材料以及在共混材料等领域的应用。     

反向原子转移自由基反应体系及其研究进展

反向原子转移自由基聚合(R-ATRP)是一种更优于传统ATRP方法的活性/可控聚合方法。本文概述了反向ATRP的反应机理,详细介绍了其反应体系的研究进展,包含聚合方法、引发剂、催化剂、单体等方面,并对反向原子转移自由基聚合研究的发展方向进行了展望。     

可控／活性自由基聚合制备含氟聚合物研究进展

介绍了几种含氟聚合物可控／活性自由基聚合制备方法的原理、优缺点和研究进展,包括碘转移聚合、氮氧自由基聚合、原子转移自由基聚合、可逆加成-断裂链转移聚合等。认为碘转移聚合在聚合工艺、产物结构控制等方面相对其他几种聚合方法有明显的优势,已工业化应用。但存在相对分子质量分布宽、链转移剂对光热敏感等不足,借助可逆碘转移聚合体系等有望解决这些缺点。     

C60有机化学反应研究概述

Ｃ６０有机化学反应介当前化学领域一个研究热点之一，已有许多具有应用前景的Ｃ６０衍生物被相继合成出来，从有机反应的角度，概述了Ｃ６０衍生物合成中的几个主要反应类型。     

桐油及其衍生物的改性在高分子材料中的应用进展

综述了4种桐油改性方法并且介绍了桐油及其改性衍生物在高分子材料应用中的主要进展.讨论了桐油的Diels-Alder反应、Friedel-Crafts反应、氧化聚合和烯烃自由基聚合改性反应及聚合机理,在此基础上,对桐油的改性方法及其在高分子材料中的应用前景进行了展望.     

Kinetic and structural studies of the polymerization of N,N′‐bismaleimide‐4,4′‐diphenylmethane with barbituric acid

Both the isothermal and non‐isothermal polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) with barbituric acid (BTA) were investigated by the differential scanning calorimeter. The experimental results showed that the polymerizations of BMI with BTA were governed by the competitive Michael addition reaction and free radical polymerization mechanisms. Furthermore, the contribution of free radical polymerization becomes more important when the mole fraction of BTA decreases. ¹H NMR and ¹³C NMR measurements further support the coexistence of the Michael addition reaction and free radical polymerization mechanisms. A preliminary kinetic model that took into account the competitive Michael addition reaction and free radical polymerization mechanisms was developed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Post‐polymerization modification by nitroxide radical coupling

Post‐polymerization modification is an attractive approach to extend applications and convert commodity plastics into products with new, desirable and tunable properties. Among the post‐polymerization modification methods, the nitroxide radical coupling (NRC) reaction has been shown to be a convenient and versatile way to graft specific functionalities onto polymer chains and to control the onset and yield of polymer crosslinking during peroxide‐initiated processes. The use of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) and its derivatives as controllers of scorch in crosslinking and as functionalizers in functionalization reactions is thoroughly described. Examples are also given of graft polymerization from macroalkoxyamines generated by NRC and grafting of nitroxides by irradiation processes. In addition, in this review we attempt to demonstrate the broad applications of the NRC reaction in the preparation of polymers with a multitude of functionalities and elaborate architectures. The examples discussed here concern the use of atom transfer and single electron transfer NRC reactions to design a variety of polymers with asymmetrical structure and the use of the radical crossover reaction, based on the alkoxyamine dynamic covalent bond, to generate reversible polymer structures and switchable functional polymers. © 2018 Society of Chemical Industry     

Benzotriazinyl‐mediated controlled radical polymerization of styrene

The stable free radical polymerization (SFRP) process based on (1,3‐diphenyl‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl), the so‐called ‘Blatter radical’, and several C‐7 substituted derivatives is introduced for the first time for the polymerization of styrene. Polystyrenes characterized by polydispersity indices in the 1.05 ? 1.27 range were obtained in the presence of the Blatter radical and its derivatives containing CF₃, Ph, Fur‐2‐yl and 4‐PhC₆H₄ substituents, while polymerization proceeded either in a non‐controlled manner or in very low polymerization yields in the presence of derivatives containing halogen (Cl, Br, I) substituents. This preliminary investigation, demonstrating the potential use of the Blatter radical and its derivatives in mediated SFRP, creates new opportunities to design and develop radicals to optimize performance in such polymerization processes. © 2013 Society of Chemical Industry     

TiCl4—C60Cln催化体系引发异丁烯正离子聚合

研究了碳笼烯非质子酸经体系引发异丁烯正离子聚合的反应规律,并与ＴｉＣｌ４正离子催体系进行了比较。ＧＰＣ的测试结果表明,ＴｉＣｌ４－Ｃ６０Ｃｌｎ催化体系中可能存在２种活性中心：（１）体系中的微量水与ＴｉＣｌ４配位形成的质子引发体系;（２）（ＴｉＣｌ５）－（Ｃ６０Ｃｌｎ－１）＾＋离子引对引发活性中心。     

Photomediated controlled radical polymerization

Photomediated controlled radical polymerization is a versatile method to prepare, under mild conditions, various well-defined polymers with complex architecture, such as block and graft copolymers, sequence-controlled polymers, or hybrid materials via surface-initiated polymerization. It also provides opportunity to manipulate the reaction through spatiotemporal control. This review presents a comprehensive account of the fundamentals and applications of various photomediated CRP techniques, including atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), nitroxide mediated polymerization (NMP) and other procedures. In addition, mechanistic aspects of other photomediated methods are discussed.     

Tunable thermal degradation and refractive index of poly(norbornene sulfone)s via two different polymerization methods

A novel polysulfone was easily synthesized by alternating copolymerization of norbornene with sulfur dioxide (SO₂) via free radical copolymerization and coordination copolymerization. Compared with other olefin derivatives, norbornene is a cyclic olefin having a larger steric hindrance, which is easily copolymerized with SO₂, and the obtained poly(norbornene sulfone)s have excellent thermomechanical and optical properties. The effect of the different polymerization methods on the copolymerization reaction was analyzed in detail. The results suggested that different polymerization mechanisms exist in the different polymerization methods and affect the thermal stability and optical properties of the polysulfone. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44534.     

High conversion study of “living” radical polymerization of styrene using DSC

The influence of temperature on nitroxide-controlled living radical polymerization of styrene was examined. It has been established that only in a temperature range of 110°C to 150°C nitroxides are able to control radical polymerization. At temperatures above 160°C the reaction was of rather a free radical character. The results were similar for all the various nitroxides used as capping agents: TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-TEMPO, 4-oxo-TEMPO and 4-acetamido-TEMPO. Differences were found only in the induction times of polymerization and were probably due to side reactions with the initiator (benzoyl peroxide). Living radical polymerization can be best controlled with these nitroxides at temperatures between 120°C and 140°C.     

Preparation and characterization of novel polymer hydrogel from industrial waste and copolymerization of poly(vinyl alcohol) and polyacrylamide

A novel hydrogel was prepared from industrial waste to form a green polymer with a higher swelling capacity. This hydrogel was synthesized by two methods for chemical crosslinking, namely crosslinking by radical polymerization and crosslinking by addition reaction. In crosslinking by radical polymerization, graft copolymerization of poly(vinyl alcohol) (PVA) and polyacrylamide (PAAm) was carried out using ceric ammonium sulfate in presence of N,N',‐methylenebisacrylamide, and then mixed with the black liquor resulting from alkaline pulping of rice straw. While, in crosslinking by addition reaction, the same above reagents were mixed with the black liquor in absence of the initiator. The black liquor is an industrial waste resulting from the pulping method and consists of dissolved lignin and carbohydrates. The black liquor causes environmental water pollution due to its dumping into the sea. The formed hydrogels were characterized using FT‐IR spectroscopy and scanning electron microscopy (SEM). It was noted that the hydrogel prepared by radical polymerization showed high swelling capacity, 60.00%, compared to that prepared by the addition reaction, 27.27%. The hydrogels formed were used also to study the influence of sodium chloride on the absorption capacity at room temperature and swelling ratios at different temperatures and pHs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012